Synthesis, Characterization, and Light Sensitivity in Titanium Piano Stool Alkyl and Sulfur Complexes, [(C(5)Me(5))TiMe(2)R] (n-) (R = Me, SCPh(3), S; n = 0, 1)

The piano stool complex (C(5)Me(5))-TiMe(3), 1, reacts with HSCPh(3) to produce (C(5)Me(5))-TiMe(2)(SCPh(3)), 2. Reduction of 2 with an alkali metal (K or Na) produces the sulfide complexes [K-(crypt)]-[(C(5)Me(5))-TiMe(2)(S)], 3-K-(crypt), and (C(5)Me(5))-TiMe(2)(μ-S)-M-(18-crown-6), 3-M-(18c6) (M = K, Na). 3-K-(crypt) is the first example of a piano stool titanium complex featuring a terminal sulfide. Compounds 1-3 are photosensitive, with photolysis experiments, monitored through (1)H NMR and UV-visible spectroscopies, demonstrating 1 as the most photostable and 3 as the least photostable.